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Register a new userExcited configurations of hydrogen in the BaTiO$_{3-x}$H$_x$ perovskite lattice associated with hydrogen exchange and transport
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Excited configurations of hydrogen in the oxyhydride BaTiO$_{3-x}$H$_x$ ($x=0.1-0.5$), which are considered to be involved in its hydrogen transport and exchange processes, were investigated by positive muon spin relaxation ($mu^+$SR) spectroscopy using muonium (Mu) as a pseudoisotope of hydrogen. Muons implanted into the BaTiO$_{3-x}$H$_x$ perovskite lattice were mainly found in two qualitatively different metastable states. One was assigned to a highly mobile interstitial protonic state, which is commonly observed in perovskite oxides. The other was found to form an entangled two spin-$frac{1}{2}$ system with the nuclear spin of an H$^-$ ion at the anion site. The structure of the (H,Mu) complex agrees well with that of a neutralized center containing two H$^-$ ions at a doubly charged oxygen vacancy, which was predicted to form in the SrTiO$_{3-delta}$ perovskite lattice by a computational study [Y. Iwazaki $et$ $al$., APL Materials 2, 012103 (2014)]. Above 100 K, interstitial Mu$^+$ diffusion and retrapping to a deep defect were observed, which could be a rate-limiting step of macroscopic Mu/H transport in the BaTiO$_{3-x}$H$_x$ lattice.
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We present low-temperature anelastic and dielectric spectroscopy measurements on the perovskite ionic conductor BaCe(1-x)Y(x)O(3-x/2) in the protonated, deuterated and outgassed states. Three main relaxation processes are ascribed to proton migration, reorientation about an Y dopant and tunneling around a same O atom. An additional relaxation maximum appears only in the dielectric spectrum around 60 K, and does not involve H motion, but may be of electronic origin, e.g. small polaron hopping. The peak at the lowest temperature, assigned to H tunneling, has been fitted with a relaxation rate presenting crossovers from one-phonon transitions, nearly independent of temperature, to two-phonon processes, varying as T^7, to Arrhenius-like. Substituting H with D lowers the overall rate by 8 times. The corresponding peak in the dielectric loss has an intensity nearly 40 times smaller than expected from the classical reorientation of the electric dipole associated with the OH complex. This fact is discussed in terms of coherent tunneling states of H in a cubic and orthorhombically distorted lattice, possibly indicating that only H in the symmetric regions of twin boundaries exhibit tunneling, and in terms of reduction of the effective dipole due to lattice polarization.
KH2PO4 (KDP) belongs to the class of hydrogen-bonded ferroelectrics, whose paraelectric to ferroelectric phase transition is driven by the ordering of the protons in the hydrogen bonds. We demonstrate that forbidden reflections of KDP, when measured at an x-ray absorption edge, are highly sensitive to the asymmetry of proton configurations. The change of average symmetry caused by the freezing of the protons during the phase transition is clearly evidenced. In the paraelectric phase, we identify in the resonant spectra of the forbidden reflections a contribution related to the transient proton configurations in the hydrogen bonds, which violates the high average symmetry of the sites of the resonant atoms. The analysis of the temperature dependence reveals a change of relative probabilities of the different proton configurations. They follow the Arrhenius law, and the activation energies of polar and Slater configurations are 18.6 and 7.3 meV, respectively.
N{o}rskov and collaborators proposed a simple kinetic model to explain the volcano relation for the hydrogen evolution reaction on transition metal surfaces in such that $ j_0= k_0 f({Delta}G_H)$ where j_0 is the exchange current density, $f({Delta}G_H)$ is a function of the hydrogen adsorption free energy ${Delta}G_H$ as computed from density functional theory, and $k_0$ is a universal rate constant. Herein, focusing on the hydrogen evolution reaction in acidic medium, we revisit the original experimental data and find that the fidelity of this kinetic model can be significantly improved by invoking metal-dependence on $k_0$ such that the logarithm of $k_0$ linearly depends on the absolute value of ${Delta}G_H$. We further confirm this relationship using additional experimental data points obtained from a critical review of the available literature. Our analyses show that the new model decreases the discrepancy between calculated and experimental exchange current density values by up to four orders of magnitude. Furthermore, we show the model can be further improved using machine learning and statistical inference methods that integrate additional material properties
Compositionally tunable vanadium oxyhydrides Sr2VO4-xHx (x = 0 - 1) without considerable anion vacancy were synthesized by high-pressure solid state reaction. The crystal structures and their properties were characterized by powder neutron diffraction, synchrotron X-ray diffraction, thermal desorption spectroscopy, and first-principles density functional theory (DFT) calculations. The hydrogen anions selectively replaced equatorial oxygen sites in the VO6 layers via statistical substitution of hydrogen in the low x region (x < 0.2). A new orthorhombic phase (Immm) with an almost entirely hydrogen-ordered structure formed from the K2NiF4-type tetragonal phase with x > 0.7. Based on the DFT calculations, the degree of oxygen/hydrogen anion ordering is strongly correlated with the bonding interaction between vanadium and the ligands.
A new class of superparamagnetism was found in relaxor ferroelectric 2/3BiFeO$_{3}$-1/3BaTiO$_{3}$. The size of the magnetic particle, estimated from the superparamagnetic magnetization curve, coincides with the size of the polar nanoregion (PNR), which governs the relaxor ferroelectric property. This suggests that the magnetic domain is identical to the PNR. The temperature variations in the sizes of the magnetic domains and PNRs estimated by our neutron diffraction measurements support this picture. Since the same domain provides both electric and magnetic properties, strong coupling between the two properties through the domain size is expected.
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